US2507200A - Process for rendering materials water-repellent and compositions therefor - Google Patents

Process for rendering materials water-repellent and compositions therefor Download PDF

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US2507200A
US2507200A US57734145A US2507200A US 2507200 A US2507200 A US 2507200A US 57734145 A US57734145 A US 57734145A US 2507200 A US2507200 A US 2507200A
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water
solution
material
salt
treated
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John R Elliott
Robert H Krieble
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General Electric Co
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/13Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • C08L83/08Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/907Resistant against plant or animal attack
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/01Silicones

Description

Patented May 9, 195.

PROCESS FOR RENDERING MATERIALS WATER-BEPELLENT AND COMPOSITIONS THEREFOR John R. Elliott and Robert H. Krieble, Schenectally, N. Y., assig'nors to General Electric Company, a corporation of New York No Drawing. Application February 10, 1945, Serial No. 577,341

Claims.

The present invention relates broadly to the treatment of materials. More particularly it is concerned with the production of water-repellent materials by treating solid bodies which are normally water-non-repellent with a composition comprising a water-soluble siliconate.

A rapid and economical method of treating materials to waterproof them is described in U. S. Patent 2,306,222, issued to Winton I. Patnode, and assigned to the same assignee as the present invention. In accordance with the methods described therein, solid bodies which normally are wetted by water (that is, water-non-repellent bodies) are contacted with an organosilicon halide (or mixture of .organosilicon halides) in vapor form. The thus treated bodies are then brought into contact with an alkaline reagent, for example, ammonia, to neutralize any acid that may be present as a result of the treatment of the bodies with the organosilicon halide.

Although exceptionally water-repellent products are obtained by the method involving the use of organosilicon halides, it has been diflicult without controlled neutralization to maintain the original tensile strength of treated cellulosic materials such as cloth and paper due to the efiect thereon of the hydrochloric or other halogen acid evolved when the organosilicon halides react with the moisture or the hydroxyl groups of the cellulose or with the moisture of the air after treatment.

The present invention is based on the discovery that by treating water-non-repellent materials with compositions containing water-soluble siliconates, products can be obtained possessing all the desirable water-repellent properties of similar materials treated with organosilicon halides and in addition, in the case of cellulosic materials, exhibiting little or no loss in strength as a result of the treatment.

The alkali siliconates employed in the practice of the present invention are prepared from siliconic acids, monoorganosilanetriols, or their condensation products and are described, for example, by Meads and Kipping, Journal of Chemical Society, 105, 679. Whereas it appears that the so-called siliconic acids generally are only hypothetical compounds, there is considerable evidence that when their condensaticn products, the polysiloxanes, are dissolved in a solution of a strong water-soluble base, the resultant solutions do contain the salts of these acids.

The siliconates can be prepared, for example, by hydrolyzing derivatives of a monohydrocarbon-substituted silane containing three hydrolyzable radicals such as halogen atoms, alkoxy groups, etc., connected to silicon, recovering the hydrolysis products, and dissolving these products in a solution of a strong inorganic base, i. e., a solution of the bases of the alkali metals and of barium, calcium, and strontium, in such proportions that there is at least one equivalent of base per silicon atom. The resultant solution containing the soluble siliconate is diluted to the desired concentration, partially neutralized if desired, and is applied to the water-non-repellent materials by dipping, spraying, or other suitable means. The treated material is thereafter dried, preferably under mildly acid condition. The treated products are highly water-repellent. In the case of porous materials no substantial reduction in porosity is noted. In general, an after-washing of treated materials further improves the water-repellent properties thereof, although such washing is not essential to the practice of the present invention. A particular advantage of the present method is its simplicity and freedom from acidic by-products which renders it suitable for general applications without employing any special equipment for handling or disposing of acid vapors, etc.

In order that those skilled in the art may better understand how the present invention may be carried into efieot, the following illustrative examples are given:

Example 1 One mol of methyltrichlorosilane was hydrolyzed by being rapidly added to a violently stirred mixture of 1 kg. crushed ice and 1 kg. of water. The resultant solution was allowed to stand until substantially all the polymonomethylsiloxanes were precipitated in the form of a fine powder. This powder was filtered from the remaining solution and dissolved by shaking with 200 cc. of 5 normal aqueous sodium hydroxide. The resultant alkaline solution was stable, although the polysiloxane resin could be precipitated from the solution by acids including such weak acids as carbon dioxide and disodium acid phosphate.

' The above solution was diluted to a concentration of between 0.05 and 1.0 molar with respect to the sodium methylsiliconate. Various types of cellulose fiber materials such as cloth and paper, when impregnated with this dilute solution and dried in air at room temperature, became highly repellent to water with substantially no reduction in porosity. When the drying process was accelerated by placing the treated materials in an oven held at elevated temperatures, some reduction in the water-repellency resulted. However, this result could be avoided either by partially neutralizing the sodium siliconate solution with a dilute acid Just prior to treatment of the cellulosic material or by neutralizing the solution after application, for example by contacting the treated material with a, gas rich in carbon dioxide. A further improvement in the waterrepellency of the treated materials was obtained by a short washing thereof with a dilute aqueous soap solution followed by several rinses with clear water.

An alternative method of rendering paper water-repellent comprises the addition of the dilute soluble siliconate to the paper pulp during the beating process. By this method the individual fibers are rendered water-repellent and this property is carried through into the final sheet.

Example 2 One mol of ethyltrichlorosilane was run into a well stirred mixture of 1 kg. ice and 1 kg. water over a period of about 2 minutes. When the stirring was stopped at the end of the addition, a clear so] formed which rapidly grew turbid and began to precipitate large white flakes of ethylpolysiloxane. The precipitate was filtered from the remaining solution and dissolved in a solution of 1 mol sodium hydroxide in a mixture of 200 cc. water and 100 cc. 95% alcohol. The alcohol was found to facilitate the solution of the ethylpolysiloxane.

Approximately six parts by volume of this 3.4 molar sodium ethylsiliconate solution was diluted with 100 parts water. A cotton poplin cloth was immersed in the solution for one minute, dried by being exposed to air at room temperature for several hours, and was then washed with a dilute soap solution, rinsed and dried in an oven maintained at a temperature of around 100 C. The treated cloth was substantially unchanged in handle or appearance, and was found to be highly water-repellent. A piece of filter paper dipped into the same solution and air dried in the same manner would no longer absorb water and retained its tensile strength after immersion in water.

Example 3 One mol of phenyltrichlorosilane was run rapidly into a violently stirred slurry of 1 kg. chopped ice and 1 kg. of water. The resultant solution soon began to deposit an insoluble phenylpolysiloxane as a sticky white solid. After standing overnight the aqueous phase was decanted and the solid dissolved in a solution of 1 mol potassium hydroxide in a mixture of 200 cc. 95% alcohol and 50 cc. water. The resultant potassium phenylsiliconate was diluted to 0.2 molar concentration with water to form a turbid colloidal solution. When a water-ethyl alcohol mixture containing 60 per cent by volume alcohol was used as the diluent a clear solution was ob tained. Cotton poplin cloth immersed in either the turbid or the clear solution, and thereafter washed and again dried as described in Example 2, was found to be water-repellent and somewhat stifier than the untreated cloth, but was otherwise unchanged in appearance or physical properties; Similar results were obtained by treating filter paper in like manner.

Example 4 Fifteen grams (0.05 mol) of barium hydroxide hydrate was dissolved in water and heated under matter. On treatment of this solution with ammonium chloride the silicone separated as an acid insoluble precipitate. Cellulosic materials dipped in the barium siliconate solution and dried were highly repellent to water.

In a like manner the siliconates of calcium and strontium may be prepared and applied to waternon-repellent materials.

It has also been found that treated cellulosic materials having a much softer texture than either the untreated materials or those treated with the unmodified siliconates can be obtained by use of a treating solution containing in addition to the siliconate a solution of a diorganosilanediol or its corresponding silicone condensation product in a strong base. These modifiers, which are believed to consist essentially of diorganosiliconeates, i. e., salts of the diorganosilanediols and the strong base, may be prepared in a manner similar to that used in preparing the siliconates, that is, by dissolving in caustic solution a silicone containing the recurring structural unit Example 5 One-half mol of dimethyldichlorosilane was run into an agitated externally cooled solution of 1.5 mols sodium hydroxide in gm. water. The resultant product was filtered to remove the precipitated sodium chloride and the filtrate was found to consist of an oily layer of dimethylsilicone and an aqueous phase. After separation of the oily layer, the aqueous phase was found to contain about 2 mols of alkali per dimethylsilicone unit, i. e. per silicon atom, and was believed to comprise the sodium salt of dimethylsilanediol, i. e. a sodium dimethylsiliconeate.

An alternative method of preparing these si'iconeates comprises dissolving the oily silicone in an alcoholic solution of potassium hydroxide .or equivalent alkali in the ratio of at least one mol of the alkali hydroxide per silicon atom.

In general the solutions comprising organosilicone units containing two hydrocarbon radicals connected to each silicon atom are not as stable as the corresponding siliconates. Their stability can be improved either by employing the base in an equivalence ratio in excess of one equivalent per silicon atom, or by use of an alcoholic solution of the alkalis, or both.

The modifiers (i. e., the metallic salt of the dihydrocarbon-substituted silanediolsi prepared from the silicones can be used in various proportions with the soluble siliconates. In general the greater the proportion of the silicone products,

the softer the feel or handle of the treated cloth or other fibrous material. Satisfactory results have been obtained when the solutions contained as high as 80 to 90 mol per cent of the modifier mentioned above and to 20 mol per cent of the soluble siliconates, the mol percentage of the modifier being calculated on the theory that it was present primarily as the mono-basic salt of the diorganosilanediol. For example. a solution of 0.25 mol sodium methylsiliconate and 0.25 mol of the sodium salt of diethylsilicol was partially neutralized by the addition of 0.25 mol of dilute sulphuric acid and was thereafter applied to cotto'n poplin cloth. The treated cloth was dried in a current of room air and was then heated for 10 minutes at 100 degrees C. The resultant products were completely water-repellent. Washing with dilute soap solution followed by a clear water rinse further improved their water-repellency. Similar results were also obtained with treating solutions wherein the sodium methylsiliconate and the modifying siliconeate were present in different proportions. The only difference in the treated products being in the feel or handle of the cloth which became softer as the relative proportions of the siliconeate was increased.

Although the present invention is particularly adapted to the treatment of cellulosic fibrous materials, it may also be employed with other waternon-repellent bodies, such as glass, porcelain, and other ceramics, wood, asbestos, etc., to render such materials water-repellent. The procedure is the same as that employed in the treatment of cellulosic materials.

While a siliconate of 'a strong base is an essential ingredient of the composition employed in the practice of the present invention, it is not necessarily the sole metal component thereof. It has been found that other metal ions in what appear to be complex metallc-siliconates can be prepared by the addition of salts of metals such as iron, lead, zinc, silver, and copper to the soluble siliconates. Many of these are useful in water-repellency applications. The products obtained by addition of soluble copper salts to alkali siliconates in less than molar proportions are particularly useful in that cellulosic materials treatved with such products are not only water-repellent but are also mildew resistant. The preparation of such treating solutions and their application to cellulosic materials is illustrated in the following example:

Example 6 A 0.4 molar solution of sodium methylsiliconate was mixed with a solution of copper sulphate in the ratio of 10 mol per cent copper sulphate per mol sodium methylsiliconate. The resultant product was a clear deep blue solution. The fact that no copper hydroxide was precipitated indicated the formation of a complex sodium coppersiliconate. Cotton cloth when treated with this solution following the procedure set forth in Example 1 possessed the same degree of water-repellency as cotton cloth treated with the unmodified sodium methylsiliconate. Neither its waterrepellency nor tensile strength was essentially affected by burial for days in garden soil. In contrast an untreated sample of the same cloth was practically decomposed by 15 days burial, while cloth treated with the unmodified sodium methylsiliconate had lost practically all its tensile strength but not its water-repellency after burial for the same length of time.

While the invention has been described with specific reference to the treatment of textiles, paper, glass, etc., with siliconates wherein the hydrocarbon radicals attached to silicon are methyl, ethyl, or phenyl radicals. it will be obvious that siliconates containing lower alkyl or aryl radicals other than these specific radicals may also be employed. In general, from the standpoint of solubility and ease of manipulation the lower alkyl siliconates, particularly the sodium or potassium methylsiliconates, are preferred. Likewise modifiers other than the sillconeates obtained from dimethylsilicone can also 'be employed. Examples of other suitable modifiers are those obtained by dissolving the diethyl, dipropyl, diphenyl, methyl ethyl, methylphenylsilicones and the like in aqueous or alcoholic solutions of sodium hydroxide, potassium hydroxide, or other strong bases.

It is to be understood also that such modifiers may be employed with soluble siliconates or the complex metallo-siliconates containing the same or different Si-hydrocarbon radicals, the selection depending to some extent on the relative stability and solubility of the modifier with reference to the particular siliconate or siliconates employed. The modified solutions obviously may be prepared by solution in a strong base of the products obtained by cohydrolysis of the mixed silanes such as a mixture of methyltrichlorosilane and dimethyldichlorosilane.

In general best results appear to be obtained when the treating solutions are of a concentration of from about 0.5 to 1.0 molar with respect to the siliconate or the total silicon units in a mixture of soluble siliconates and siliconeates. However, the invention is not limited to these proportions as acceptable products have been obtained with treating solution concentrations ranging from approximately 0.01 molar to more than 5 molar depending to some extent on the amount of solution picked up and retained by the material being treated. With solutions of higher concentrations, care should be taken to avoid gross flocculation of the polysiloxanes on the base material as such flocs impart no water-repellency. The usual precaution to be taken is to dry rapidly with high velocity air at low wet bulb temperatures.

What we claim as new and desire to secure by Letters Patent of the United States is:

1. The process of rendering a non-waterrepellent material water-repellent which comprises (1) treating said material with a composition comprising an aqueous solution of a watersoluble metallic salt of a hydrocarbon-substituted silanetriol, the metal ion of said salt being a member selected from the class consisting of alkali metals and alkaline earth metals, and (2) causing the formed hydrocarbon-substituted polysiloxane on the surface of the treated material to become water-insoluble by drying the treated material under mildly acidic conditions whereby the treated material becomes water-repellent.

2. The process of rendering a non-waterrepellent material water-repellent which comprises (1) treating said material with a composition comprising (a) an aqueous solution of a water-soluble metallic salt of a hydrocarbonsubstituted silanetriol, the metal ion of said salt being a member selected from the class consistin of alkali metals and alkaline earth metals and (b) an inorganic water-soluble salt of a metal selected from the class consisting of iron, lead, zinc, silver and copper, and (2) causing the formed hydrocarbon-substituted polysiloxane on the surface of the treated material to become water-insoluble by drying'the treated material under mildly acidic conditions whereby the treated material becomes water-repellent.

3. The process of rendering a non-waterrepellent material water-repellent which comprises (l) treating said material with a composition comprising an aqueous solution containing (a) from 10 to 50 mol per cent of a water-soluble metallic salt of a hydrocarbon-substituted silanetriol and (b) from 50 to 90 mol per cent of a water-soluble metallic salt of a dihydrocarbonsubstituted silanediol, the metal ion of the said metallic salts of (a) and (b) being a member selected from the class of alkali metals and alkaline earth metals, and (2) causing the formed hydrocarbon-substituted polysiloxanes on the surface of the treated material to become waterinsoluble by drying the treated material under mildly acidic conditions whereby the treated material becomes water-repellent.

4. The process of rendering a non-water repellent material water-repellent which comprises (1) treating said material with a composition comprising an aqueous solution containing (a) from 10 to 50 mol per cent of a water-soluble alkali-metal salt of methylsilanetriol and (b) from 50 to 90 mol per cent of a water-soluble alkali-metal salt of dimethylsilanediol, and (2) causing the formed methylpolysiloxanes on the surface of the treated material to become waterinsoluble by drying the treated material under mildly acidic conditions whereby the treated material becomes water-repellent.

5. The process of rendering a cellulosic material water-repellent which comprises (I) treating said material with a composition comprising an aqueous solution of a water-soluble metallic salt of an alkyl-substituted silanetriol, the metal ion of the said salt being a member selected from the class consisting of alkali metals and alkaline earth metals, and (2) causing the formed alkyl polysiloxane on the surface of the treated material to become water-insoluble by drying the treated material under mildly acidic conditions whereby the treated material becomes waterrepellent.

6. The process of claim 5 wherein the metal ion of the metallic salt is barium.

7. The process of rendering a cellulosic material water-repellent and fungus resistant which comprises (1) treating said material with a composition comprising (a) an aqueous solution of a water-soluble alkali-metal salt of methylsilanetriol and (b) a water-soluble inorganic copper salt, and (2) causing the formed methylpolysiloxane on the surface of the treated material to become water-insoluble by drying the treated material under mildly acidic conditions whereby the treated material becomes waterrepellent.

8. The process of rendering a cellulosic material water-repellent which comprises (I) treating said material with a composition comprising an aqueous solution containing (a) from to 50 mol per cent of a water-soluble alkali-metal salt of methylsilanetriol and (b) from 50 to 90 mol per cent of a water-soluble alkali-metal salt of dimethylsilanediol, and (2) causing the formed methylpolysiloxanes on the surface of the treated material to become water-insoluble by drying the treated material under mildly acidic conditions whereby the treated material becomes waterrepellent.

9. The process of rendering a cellulosic material water-repellent which comprises (1) treating said material with a composition comprising an aqueous solution of (a) from 10 to 50 mol per cent of a water-soluble alkali-metal salt of methylsilanetriol and (b) from 50 to mol per cent of a water-soluble alkali-metal salt of dimethylsilanediol, and (2) causing the formed methylpolysiloxanes on the surface of the treated material to become water-insoluble by drying the treated material under mildly acidic conditions comprising an atmosphere of carbon dioxide whereby the treated material becomes waterrepellent.

10. A composition for rendering materials water-repellent and for improving the feel of said materials, said composition comprising an aqueous solution containing (1) from 10 to 50 mol per cent of a water-soluble metallic salt of a hydrocarbon-substituted silanetriol, (2) from 50 to 90 mol per cent of a water-soluble metallic salt of a dihydrocarbon-substituted silanediol, each metal ion of the metallic salts in (1) and (2) being a member selected from the class consisting of alkali metals and alkaline earth metals, and (3), in combination therewith, a watersoluble inorganic copper salt in an amount equal to 10 mol per cent based on the metallic salt of the silanetriol.

11. A composition for rendering materials water-repellent and for improving the feel of said materials, said composition comprising (1) from 10 to 50 mol per cent of a water-soluble alkalimetal salt of a hydrocarbon-substituted silanetriol and (2) from 50 to 90 mol per cent of a water-soluble alkali-metal salt of a dihydrocarbon-substituted silanediol.

12. A composition for rendering materials water-repellent and for improving the feel of said materials, said composition comprising an aqueous solution comprising (1) from 10 to 50 mol per cent of a water-soluble alkali-metal salt of a hydrocarbon-substituted silanetriol, (2) from 50 to 90 mol per cent of a water-soluble alkalimetal salt of a dihydrocarbon-substituted silanediol, and (3) an inorganic water-soluble copper salt, the ingredients (1), (2) and (3) being dis solved in the said solution.

13. A composition for rendering materials water-repellent and for improving the feel of said materials, said composition comprising an aqueous solution containing (1) from 10 to 50 mol per cent of a water-soluble metallic salt of an alkylsilanetriol, (2) from 50 to 90 mol per cent of a water-soluble metallic salt of a dialkylsilanediol, the metal ions of (l) and (2) each being a member selected from the class consisting of alkali metals and alkaline .earth metals, and (3) an inorganic water-soluble metal salt, the metal ion of which is a member selected from the class consisting of copper, zinc, iron, lead, and silver.

14. A composition for rendering materials water-repellent and for improving the feel of said materials, said composition comprising an aqueous solution containing (1) from 50 to 90 mol per cent of a water-soluble alkali-metal salt of dimethylsilanediol, (2) from 10 to 50 mol per cent of a water-soluble metallic salt of methylsilanetriol wherein the metal ion of the metallic salt is a member selected from the class consisting of alkali metals and alkaline earth metals, and (3) a water-soluble inorganic metal salt wherein the metal ion is a member selected from the class consisting of copper, zinc, iron, lead, and silver.

15. A composition for rendering materials water-repellent and for improving the feel of said materials, said composition comprising an aqueous solution containing (1) from 10 to 50 mol per cent of a water-soluble sodium salt of methylsilanetriol, (2) from 50 to 90 mol per cent of a water-soluble sodium salt of dimethylsilanediol, and (3) an inorganic water-soluble copper salt.

JOHN R. ELLIOTT. ROBERT H. KRIEBLE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Gender July 14, 1874 Number OTHER REFERENCES Meads et 2.1.: J. Chem. Soc. (London), vol. 105, 1914, pp. 679, 684 and 688.

Meads et 111.: J. Chem. Soc. (London), vol. 107, 1915, Pp. 459, 465 and 468.

Stock et 91.: Berichte Deut. Chem. Geseh, vol.

52, 1919, pages 695, 708 and 723.

Chem. and Engineering News, Vol. 24, No. 9. May 10, 1946, pages 1233 and 1234.

Claims (2)

1. THE PROCESS OCC RENDERING A NON-WATERREPELLENT MATERIAL WATER-REPELLENT WHICH COMPRISES (1) TREATING SAID MATERIAL WITH A COMPOSITION COMPRISING AN AQUEOUS SOLUTION OF A WATERSOLUBLE METALLIC SALT OF A HYDROCARBON-SUBSTITUTED SILANETRIOL, THE METAL ION OF SAID SALT BEING A MEMBER SELECTED FROM THE CONSISTING OF ALKALI METALS AND ALKALINE EARTH METALS, AND (2) CAUSING THE FORMED HYDROCARBON-SUBSTITUTED POLYSILOXANE ON THE SURFACE OF THE TREATED MATERIAL TO BECOME WATER-INSOLUBLE BY DRYING THE TREATED MATERIAL UNDER MILDLY ACIDIC CCONDITIONS WHEREBY THE TREATED MATERIL BECOMES WATER-REPELLENT.
10. A COMPOSITION FOR RENDERING MATERIALS WATER-REPELLENT AND FOR IMPROVING THE FEEL OF SAID MATERIALS, SAID COMPOSITION COMPRISING AN AQUEOUS SOLUTION CONTAINING (1) FROM 10 TO 50 MOL PER CENT OF A WATER-SOLUBLE METALLIC SALT OF A HYDROCARBON-SUBSTITUTED SILANETRIOL, (2) FROM 50 TO 90 MOL PER CENT OF A WATER-SOLUBLE METALLIC SALT OF A DIHYDROCARBON-SUBSTITIUTED SILANEDIO!, EACH METAL ION OF THE METALLIC SALTS IN (1) AND (2) BEING A MEMBER SELECTED FROM THE CLASS CONSISTING OF ALKALI METALS AND ALKALINE EARTH METALS, AND (3), IN COMBINATION THEREWITH, A WATERSOLUBLE INORGANIC COPPOR SALT IN AN AMOUNT EQUAL TO 10 MOL PER CENT BASED ON THE METALLIC SALT OF THE SILANETRIOL.
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DE966699C (en) * 1953-06-03 1957-09-05 Max G Becker Dipl Chem Adhesive on the basis of water glass
US2813085A (en) * 1954-01-27 1957-11-12 Cowles Chem Co Aqueous cementitious composition containing an alkali metal silanol salt
US2816610A (en) * 1954-08-02 1957-12-17 Phillips Petroleum Co Minimizing water flow into oil wells
DE1023462B (en) * 1955-01-21 1958-01-30 Union Carbide Corp A process for preparing Alkoxysilylpropylaminen
DE1031910B (en) * 1952-05-27 1958-06-12 Gen Electric Aqueous paint, in particular casein, rubber latex or alkyd paint oelmodifizierte
DE1060566B (en) * 1952-04-01 1959-07-02 Libbey Owens Ford Glass Co A method for water-repellency to form structures which can react with silanols on its surface due to the presence of hydroxyl groups, eg. B. A shaped glass
US2898221A (en) * 1957-05-06 1959-08-04 Dow Corning Concrete of improved strength
US2905562A (en) * 1957-07-29 1959-09-22 Gen Electric Process for rendering masonry water-repellent
US2930717A (en) * 1957-02-01 1960-03-29 American Viscose Corp Non-blocking pellicle and method for making the same
US2937155A (en) * 1957-03-01 1960-05-17 American Cyanamid Co Composition containing alkyl silane triol and aminoplast resin and article coated therewith
US2937580A (en) * 1960-05-24 Treated highway surfaces
US2946707A (en) * 1954-09-30 1960-07-26 Harold H Sperber Storage batteries and fluids therefor
US2961339A (en) * 1953-03-27 1960-11-22 Ivan A Wolff Free flowing, hydrophobic granular starch and method of making the same
US3018270A (en) * 1960-07-28 1962-01-23 Union Carbide Corp Process for producing silicone resins
US3057821A (en) * 1962-10-09 Ammonium halide stabilized organo-
US3071492A (en) * 1953-10-07 1963-01-01 Standard Brands Inc Method of rendering starch hydrophobic and free flowing
US3110614A (en) * 1962-12-11 1963-11-12 Prismo Safety Corp Treatment of glass beads with methyl hydrogen polysiloxane
US3120500A (en) * 1961-07-10 1964-02-04 Union Carbide Corp Process for producing silicone resins of controlled hydroxyl content
US3137100A (en) * 1953-04-29 1964-06-16 Norman P Harshberger Roofing product
DE1205440B (en) * 1959-07-21 1965-11-18 Wacker Chemie Gmbh Water repellents for materials and components
DE1205374B (en) * 1959-09-08 1965-11-18 Dow Corning The coating color for the preparation of water-repellent art papers
US3335017A (en) * 1962-03-14 1967-08-08 Warren S D Co Paper with release coating and process for making same
US3348991A (en) * 1962-12-20 1967-10-24 Rogers Corp Method of making a waterproof gas-permeable plastic sheet
US3438807A (en) * 1965-12-15 1969-04-15 Union Carbide Corp Silicone sized paper and cellulosic fiber
US3628986A (en) * 1969-08-22 1971-12-21 Exxon Research Engineering Co Water-repellent reduced iron ore
US3914476A (en) * 1972-05-23 1975-10-21 Wacker Chemie Gmbh Method for imparting water repellency to inorganic surfaces
US3941864A (en) * 1973-06-04 1976-03-02 Wacker-Chemie Gmbh Method for manufacturing molded structures and coatings based on inorganic binding agents
US3956570A (en) * 1972-09-19 1976-05-11 Wacker-Chemie Gmbh Method for imparting water-repellency to construction materials
US4012355A (en) * 1973-12-26 1977-03-15 The Dow Chemical Company Composition useful in preventing environmental erosion containing film forming organic polymer and silicone
US4028172A (en) * 1974-04-15 1977-06-07 National Starch And Chemical Corporation Process of making paper
US4087572A (en) * 1972-11-16 1978-05-02 The Dow Chemical Company Method of preventing environmental erosion
DE3031598A1 (en) * 1979-09-24 1981-03-26 Dow Corning Aqueous metallaminsiliconatloesungen, derived amorphous materials and their use
US4342796A (en) * 1980-09-10 1982-08-03 Advanced Chemical Technologies, Inc. Method for inhibiting corrosion of internal structural members of reinforced concrete
US4536240A (en) * 1981-12-02 1985-08-20 Advanced Semiconductor Products, Inc. Method of forming thin optical membranes
US4997461A (en) * 1989-09-11 1991-03-05 Norton Company Nitrified bonded sol gel sintered aluminous abrasive bodies
US5131923A (en) * 1989-09-11 1992-07-21 Norton Company Vitrified bonded sol gel sintered aluminous abrasive bodies
FR2744760A1 (en) * 1996-02-14 1997-08-14 Inst Francais Du Petrole Improving the recovering of hydrocarbon(s) in a porous medium
US20060107876A1 (en) * 2004-11-25 2006-05-25 Wacker-Chemie Gmbh Glycol-functional siloxane mixture
WO2007077951A3 (en) * 2005-12-28 2007-11-15 Kao Corp Fibre modified by application of an organosiliconate agent, a fibre modifying agent comprising an organosilikonate and a method of modifying a fibre with said agent
CN102633826A (en) * 2012-04-08 2012-08-15 荆州市江汉精细化工有限公司 Method for preparing propyl silicate aqueous solution by utilizing propyl trichlorosilane

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US3057821A (en) * 1962-10-09 Ammonium halide stabilized organo-
US2937580A (en) * 1960-05-24 Treated highway surfaces
US2733592A (en) * 1956-02-07 Ceramic tile
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US2646373A (en) * 1950-01-20 1953-07-21 Cowles Chem Co Treatment of papermaking fibers with organosilicon compounds
US2582215A (en) * 1950-02-23 1952-01-15 Dow Corning Method of rendering ceramic materials water repellent
US2726176A (en) * 1950-08-07 1955-12-06 Allied Chem & Dye Corp Waterproofing porous ceramic materials with ethylsiloxanol and article produced thereby
US2680073A (en) * 1951-01-10 1954-06-01 Allied Chem & Dye Corp Method of sizing paper
US2683097A (en) * 1951-04-17 1954-07-06 Owens Corning Fiberglass Corp Coating glass fibers with unsaturated polysiloxanolate and article produced thereby
DE1017132B (en) * 1951-04-17 1957-10-10 Owens Corning Fiberglass Corp A process for the finishing of glass fibers
US2799598A (en) * 1951-08-17 1957-07-16 Owens Corning Fiberglass Corp Process of forming coated twisted yarns and woven fabrics and resultant article
US2731367A (en) * 1951-12-20 1956-01-17 Owens Corning Fiberglass Corp Sized and anti-static coated synthetic fiber and process of coating
DE1060566B (en) * 1952-04-01 1959-07-02 Libbey Owens Ford Glass Co A method for water-repellency to form structures which can react with silanols on its surface due to the presence of hydroxyl groups, eg. B. A shaped glass
US2729572A (en) * 1952-05-27 1956-01-03 Gen Electric Stable solution of an aluminum salt of a methyl silane triol
US2803561A (en) * 1952-05-27 1957-08-20 Gen Electric Process for rendering calcium-containing masonry water-repellent
US2713545A (en) * 1952-05-27 1955-07-19 Gen Electric Water-base paints and process of making
DE1031910B (en) * 1952-05-27 1958-06-12 Gen Electric Aqueous paint, in particular casein, rubber latex or alkyd paint oelmodifizierte
US2711967A (en) * 1952-08-02 1955-06-28 Leandro W Tomarkin Water-repellant composition
US2760876A (en) * 1952-11-25 1956-08-28 Siliphane Corp Of America Water resistant coating compositions
US2787274A (en) * 1952-12-26 1957-04-02 Hersh Ammonium polysiloxanolate hair treating composition and method for using same
US2961339A (en) * 1953-03-27 1960-11-22 Ivan A Wolff Free flowing, hydrophobic granular starch and method of making the same
US2723211A (en) * 1953-04-13 1955-11-08 Cowles Chem Co Stable silane triol composition and method of treating glass therewith
US2791511A (en) * 1953-04-21 1957-05-07 Sonneborn Sons Inc L Substantially waterproof surfacing materials
US3137100A (en) * 1953-04-29 1964-06-16 Norman P Harshberger Roofing product
US2784139A (en) * 1953-05-28 1957-03-05 Hazel H Cutler Thixotropic wood preservation composition and process for preparing same
DE966699C (en) * 1953-06-03 1957-09-05 Max G Becker Dipl Chem Adhesive on the basis of water glass
US2774674A (en) * 1953-09-03 1956-12-18 Rhone Poulenc Sa Anti-adhesion compositions
US3071492A (en) * 1953-10-07 1963-01-01 Standard Brands Inc Method of rendering starch hydrophobic and free flowing
US2813085A (en) * 1954-01-27 1957-11-12 Cowles Chem Co Aqueous cementitious composition containing an alkali metal silanol salt
US2785145A (en) * 1954-07-01 1957-03-12 American Cyanamid Co Siliconate-aminoplast compositions and textiles coated therewith
US2816610A (en) * 1954-08-02 1957-12-17 Phillips Petroleum Co Minimizing water flow into oil wells
US2946707A (en) * 1954-09-30 1960-07-26 Harold H Sperber Storage batteries and fluids therefor
DE1023462B (en) * 1955-01-21 1958-01-30 Union Carbide Corp A process for preparing Alkoxysilylpropylaminen
US2930717A (en) * 1957-02-01 1960-03-29 American Viscose Corp Non-blocking pellicle and method for making the same
US2937155A (en) * 1957-03-01 1960-05-17 American Cyanamid Co Composition containing alkyl silane triol and aminoplast resin and article coated therewith
US2898221A (en) * 1957-05-06 1959-08-04 Dow Corning Concrete of improved strength
US2905562A (en) * 1957-07-29 1959-09-22 Gen Electric Process for rendering masonry water-repellent
DE1205440B (en) * 1959-07-21 1965-11-18 Wacker Chemie Gmbh Water repellents for materials and components
DE1205374B (en) * 1959-09-08 1965-11-18 Dow Corning The coating color for the preparation of water-repellent art papers
US3018270A (en) * 1960-07-28 1962-01-23 Union Carbide Corp Process for producing silicone resins
US3120500A (en) * 1961-07-10 1964-02-04 Union Carbide Corp Process for producing silicone resins of controlled hydroxyl content
US3335017A (en) * 1962-03-14 1967-08-08 Warren S D Co Paper with release coating and process for making same
US3110614A (en) * 1962-12-11 1963-11-12 Prismo Safety Corp Treatment of glass beads with methyl hydrogen polysiloxane
US3348991A (en) * 1962-12-20 1967-10-24 Rogers Corp Method of making a waterproof gas-permeable plastic sheet
US3438807A (en) * 1965-12-15 1969-04-15 Union Carbide Corp Silicone sized paper and cellulosic fiber
US3628986A (en) * 1969-08-22 1971-12-21 Exxon Research Engineering Co Water-repellent reduced iron ore
US3914476A (en) * 1972-05-23 1975-10-21 Wacker Chemie Gmbh Method for imparting water repellency to inorganic surfaces
US3956570A (en) * 1972-09-19 1976-05-11 Wacker-Chemie Gmbh Method for imparting water-repellency to construction materials
US4087572A (en) * 1972-11-16 1978-05-02 The Dow Chemical Company Method of preventing environmental erosion
US3941864A (en) * 1973-06-04 1976-03-02 Wacker-Chemie Gmbh Method for manufacturing molded structures and coatings based on inorganic binding agents
US4012355A (en) * 1973-12-26 1977-03-15 The Dow Chemical Company Composition useful in preventing environmental erosion containing film forming organic polymer and silicone
US4028172A (en) * 1974-04-15 1977-06-07 National Starch And Chemical Corporation Process of making paper
DE3050752C2 (en) * 1979-09-24 1989-05-11 Dow Corning Corp., Midland, Mich., Us
DE3031598A1 (en) * 1979-09-24 1981-03-26 Dow Corning Aqueous metallaminsiliconatloesungen, derived amorphous materials and their use
US4400326A (en) * 1979-09-24 1983-08-23 Dow Corning Corporation Aqueous metal ammine siliconate solutions, and amorphous materials derived therefrom, and methods of their use
US4342796A (en) * 1980-09-10 1982-08-03 Advanced Chemical Technologies, Inc. Method for inhibiting corrosion of internal structural members of reinforced concrete
US4536240A (en) * 1981-12-02 1985-08-20 Advanced Semiconductor Products, Inc. Method of forming thin optical membranes
US4997461A (en) * 1989-09-11 1991-03-05 Norton Company Nitrified bonded sol gel sintered aluminous abrasive bodies
US5131923A (en) * 1989-09-11 1992-07-21 Norton Company Vitrified bonded sol gel sintered aluminous abrasive bodies
FR2744760A1 (en) * 1996-02-14 1997-08-14 Inst Francais Du Petrole Improving the recovering of hydrocarbon(s) in a porous medium
US20060107876A1 (en) * 2004-11-25 2006-05-25 Wacker-Chemie Gmbh Glycol-functional siloxane mixture
WO2007077951A3 (en) * 2005-12-28 2007-11-15 Kao Corp Fibre modified by application of an organosiliconate agent, a fibre modifying agent comprising an organosilikonate and a method of modifying a fibre with said agent
CN101346511B (en) 2005-12-28 2012-12-19 花王株式会社 Fiber modified by organic silicate reagent, fiber modifying agent containing organic silicate and method for modifying fiber by the reagent
CN102633826A (en) * 2012-04-08 2012-08-15 荆州市江汉精细化工有限公司 Method for preparing propyl silicate aqueous solution by utilizing propyl trichlorosilane

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